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Measurement Science Review     Open Access   (Followers: 1)
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Journal Cover Reactive and Functional Polymers
   Journal TOC RSS feeds Export to Zotero [6 followers]  Follow    
   Hybrid Journal Hybrid journal (It can contain Open Access articles)
     ISSN (Print) 1381-5148
     Published by Elsevier Homepage  [2563 journals]   [SJR: 0.834]   [H-I: 55]
  • Synthesis of Perylene Dianhydride-incorporated Main Chain Polyimides and
           Sequential Structural Transformation through a Dipolar Cycloaddition
    • Abstract: Publication date: Available online 10 September 2014
      Source:Reactive and Functional Polymers
      Author(s): Mieon Choi , Jung Yun Do
      Perylene dianhydride (PDA)-incorporated polyimides were prepared. The perylene unit in the polyimide was thermally converted to the corresponding N-heterocyclic polyarene unit through a Diels-Alder reaction. The monomer, 2,2-bis(3-amino-4-hydroxyphenyl) hexafluoropropane (6FAP), was modified via O-alkylation to improve the solubility of the polymer. 2-Ethylhexyl-attached 6FAP yielded a soluble copolyimide that contained ca. 70 mol% PDA using pyromellitic dianhydride. The perylene unit of the copolyimide transformed to a polyarene unit through the dipolar cycloaddition of 4-aryl-1,2,4-triazole-3,5-dione (TAD) and maleic anhydride. The perylene transformation of the polyimide occurred with 50% conversion with maleic anhydride and quantitatively with TAD. The PDA-copolymer exhibited a spectral blue-shift and red-shift by maleic anhydride and TAD, respectively.

      PubDate: 2014-09-13T02:55:15Z
  • Catalytic graphitization of Electrospun Cellulose Nanofibres Using Silica
    • Abstract: Publication date: Available online 9 September 2014
      Source:Reactive and Functional Polymers
      Author(s): Libo Deng , Anna E. Lewandowska , Robert J. Young , Guoping Zhang , Rong Sun , Stephen J. Eichhorn
      Electrospun cellulose nanofibres have been graphitized in the presence of silica (SiO2) nanoparticles. The structure of the resultant SiC/C hybrids was characterized using transmission electron microscopy, X-ray diffraction and Raman spectroscopy. Bamboo-like silicon carbide (SiC) nanostructures were observed emanating from the nanofibres treated at 1500 °C which were thought to grow through a vapor-liquid-solid process. The formation of SiC was also thought to lead to a higher degree of graphitization for the electrospun cellulose fibres. These porous and graphitized nanofibres might find applications in electrochemical energy storage.

      PubDate: 2014-09-13T02:55:15Z
  • Thin film composite nanofiltration membranes fabricated from polymeric
           amine polyethylenimine imbedded with monomeric amine piperazine for
           enhanced salt separations
    • Abstract: Publication date: Available online 6 September 2014
      Source:Reactive and Functional Polymers
      Author(s): Dihua Wu , Sanchuan Yu , Darren Lawless , Xianshe Feng
      Thin film composite (TFC) nanofiltration membranes were fabricated by interfacial polymerization using polymeric amine polyethylenimine (PEI) and monomeric amine piperazine (PIP) as the amine reactant. Membranes with a single-ply polyamide layer were produced by reacting trimesoyl chloride (TMC) with mixed amines of PEI and PIP, and incorporation of a small amount of PIP in PEI was found to increase the permeation flux effectively while still maintaining a good solute rejection. For instance, adding 10 wt% PIP in the amine reactant solution resulted in a 6-fold increase in permeation flux, while a 91.6% MgCl2 rejection was maintained. In addition, 2-ply polyamide membranes were also prepared by two cycles of PEI-TMC and PIP-TMC interfacial reactions separately, and they showed a higher rejection than the single-ply polyamide membrane. At a low PIP/PEI concentration ratio, the single-ply polyamide membranes formed with mixed amines of PIP and PEI tended to be more permeable than the 2-ply polyamide membranes. However, it was demonstrated that by properly controlling the PIP/PEI concentration ratio, the 2-ply polyamide membranes with both a higher permeation flux and salt rejection than conventional single-ply polyamide membranes could be produced. The resulting membranes were characterized for chemical composition, surface hydrophilicity, surface charge and morphology of the polyamide skin layer.

      PubDate: 2014-09-08T02:15:09Z
  • Reinforcing efficiency of nanocellulose in polymers
    • Abstract: Publication date: Available online 6 September 2014
      Source:Reactive and Functional Polymers
      Author(s): Yvonne Aitomäki , Kristiina Oksman
      Nanocellulose extracted from renewable sources, is a promising reinforcement for many polymers and is a material where strong interfibre hydrogen bonds add effects not seen in microfiber composites. Presented is a tool for comparing different nanocellulose composites based on estimating the efficiency of nanocellulose reinforcement. A reinforcing efficiency factor is calculated from reported values of elastic modulus and strength from various nanocellulose composites using established micromechanical models. In addition, for the strength, a network model is derived based on fibre-fibre bond strength within nanocellulose networks. The strength results highlight the importance of the plastic deformation in the nanocellulose composites. Both modulus and strength efficiency show that the network strength and modulus has a greater effect than that of the individual constituents. In the best cases, nanocellulose reinforcement exceeds all model predictions.

      PubDate: 2014-09-08T02:15:09Z
  • Surface modification of composite ion exchange membranes by polyaniline
    • Abstract: Publication date: Available online 3 September 2014
      Source:Reactive and Functional Polymers
      Author(s): H. Farrokhzad , M.R. Moghbeli , T. Van Gerven , B. Van der Bruggen
      The aim of this work is to develop new selective cation exchange membranes (CEMs) from bivalent to monovanet selectivity bysurface functional groups. So, a novel hybrid cation exchange membrane was prepared by polymerization of polyaniline on a composite membrane, made of polyvinylidene fluoride (PVDF) and sulfonated PVDF (S-PVDF). Polyaniline was doped with different doping agents and their effect on total salt extraction and selectivity of bivalent to monovalent cations was evaluated. The chemical and morphological properties of hybrid membranes were characterized by Fourier transform infrared spectroscopy (FTIR), X-Ray diffraction (XRD) and scanning electron microscopy (SEM). Ion exchange capacity (IEC), transport number, ion conductivity and water uptake decreased after surface polymerization. Composite membrane has a good selectivity (∼2) for bivalent and excellent removal of both cations. The hybrid membrane, doped with pTSA has a very high selectivity for monovalent ions (∼7.1) and a high removal of monovalent ions.

      PubDate: 2014-09-08T02:15:09Z
  • In situ oxidation-induced gelation of poly(aspartic acid) thiomers
    • Abstract: Publication date: Available online 6 September 2014
      Source:Reactive and Functional Polymers
      Author(s): Benjámin Gyarmati , Enikő Krisch , András Szilágyi
      In situ gelling poly(aspartic acid) thiomers are investigated to demonstrate their potential application in the development of injectable formulations. The chemical stability of the thiomer solutions is measured against air to determine the maximum storage time of the solution before injection. Hydrogels exhibit considerably large storage moduli after the chemical oxidation of the low-viscosity thiomer solution. The gelation time can be controlled within 2 to 6 min, which is advantageous for injection because the thiomer solution and the oxidizing agent can be mixed safely in a two-chamber system before injection into the desired site of the body.
      Graphical abstract image

      PubDate: 2014-09-08T02:15:09Z
  • Synthesis and characterization of chitosan hydrogels cross-linked with
           dicarboxylic acids
    • Abstract: Publication date: Available online 6 September 2014
      Source:Reactive and Functional Polymers
      Author(s): N.E. Valderruten , J. Valverde , F. Zuluaga , E. Ruiz-Durantez
      Chitosan hydrogels cross-linked with dicarboxylic acids were prepared. Succinic, glutaric and adipic acid were used as cross-linking agents, the goal being to compare the effect of the length of the chain on the behavior of the material obtained. The swelling properties were studied at different pHs and temperatures, and it was discovered that these properties depend particularly on the pH of the environment. Creep-recovery and stress-relaxation studies were performed to determine mechanical properties and the chitosan/succinic acid hydrogels exhibited a completely viscous behavior. Thermal studies were carried out using differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). DSC results revealed that the materials obtained are completely amorphous. Acetaminophen was used as a positive control for the release kinetics studies. Upon fitting the results to a specific mathematical model, it was determined that the release process is controlled by diffusion and relaxation of the polymer network.

      PubDate: 2014-09-08T02:15:09Z
  • Significance of xylan on the stability and water interactions of
           cellulosic nanofibrils
    • Abstract: Publication date: Available online 6 September 2014
      Source:Reactive and Functional Polymers
      Author(s): Tiia-Maria Tenhunen , Maria Soledad Peresin , Paavo A. Penttilä , Jaakko Pere , Ritva Serimaa , Tekla Tammelin
      In this paper, the significance of xylan on the behaviour of kraft birch pulp based nanofibrillated cellulose (CNF) is discussed. The influence of CNF xylan content on fibril morphology, charge and stability as well as on the film formation ability was investigated, and the features detected on nanoscale and on macroscale are compared. In addition to this, the ability of fibrils to uptake water molecules were investigated by bulk and surface sensitive methods which are Dynamic water sorption analysis (DVS) and Quartz crystal microbalance with dissipation monitoring (QCM-D) equipped with the humidity module, respectively. Surface xylan plays a significant role as an electrosteric stabilizer in dilute CNF dispersions when the surface forces are dominant whereas the removal of xylan drastically changes the CNF dispersion properties. The settling of the unstable CNF dispersions displays behaviour which is typical for hindered sedimentation. When considering thin nanoscale layers of CNF, nanofibrillated cellulosic materials with high content of surface xylan has somewhat higher ability to bind water molecules. However, it seems that in more concentrated CNF dispersions where the fibrillar network itself plays also a decisive role, especially with respect to film formation ability, the impact of xylan diminishes. Solvent cast macroscale CNF films are still enough dense to maintain good oxygen barrier performance at higher humid conditions although agglomeration tendency of fibrils is higher due to the excessive xylan removal. These findings are of high relevance when considering nanocellulosic materials, especially in the form of gels and films, as templates for high added value material solutions.

      PubDate: 2014-09-08T02:15:09Z
  • Nanocomposite films based on cellulose nanofibrils and water-soluble
    • Abstract: Publication date: Available online 23 August 2014
      Source:Reactive and Functional Polymers
      Author(s): Jessica Lucenius , Kirsti Parikka , Monika Österberg
      All-polysaccharide composite films were prepared from native, unmodified cellulose nanofibrils (CNF) mixed with various natural water-soluble polysaccharides like carboxymethyl cellulose, galactoglucomannan, xyloglucan and guar gum. Composite films were manufactured by pressurized filtration and hot pressing. The mechanical properties of the films were systematically evaluated in the dry and the wet state. GG was furthermore selectively oxidized using galactose oxidase (EC, and the effect of the degree of oxidation on the final composite film properties was shown. It was found that all the tested polysaccharides increased the strength and toughness of the dry composite films at 2 weight percent (wt-%) addition to CNF. After soaking the samples for 24h in water, striking differences between the samples were found: already at 2 wt-% CMC the wet strength of the composite films diminished, while the uncharged polysaccharides improved the wet strength. For example, the addition of 2 wt-% GGM increased Young’s modulus by a factor of 1.3, the tensile strength by a factor of 2.8, and the toughness by a factor of 3.4. The results are discussed in relation to the amount of water absorbed in the films and possible reasons for the improved properties are suggested.

      PubDate: 2014-09-03T00:59:50Z
  • Ion-Fuelled L-Phenylalanine Controlled Pumping by Hybrid Membrane
    • Abstract: Publication date: Available online 27 August 2014
      Source:Reactive and Functional Polymers
      Author(s): Pascal Blondeau , Mihail Barboiu , Eddy Petit
      We report organic-inorganic membrane materials for controlled translocation of ion-pairs along directional conduction pathways. The supramolecular/sol-gel combined procedure has been realised in two steps. First, the self-organization properties of 3-(ureidoarene)propyltriethoxysilane compound, 1 in aprotic solvents were determined, revealing the formation of supramolecular oligomers, in the self-assembly step. They led in a second sol-gel transcription step to hybrid membrane materials. Then, the transport of organic molecules of variable charge, like L-Phenylalanine can be directionally tuned, via ion-fuelled membrane polarization phenomena. Using this strategy, the transport of the cationic, zwitterionic and anionic forms of the L-Phenylalanine can be controlled and directionally oriented from the feed to strip phase and vice versa.

      PubDate: 2014-09-03T00:59:50Z
  • Influence of molecular weight of polydimethylsiloxane precursors and
           crosslinking content on degree of ethanol swelling of crosslinked networks
    • Abstract: Publication date: Available online 27 August 2014
      Source:Reactive and Functional Polymers
      Author(s): Wanqiu Zhang , Xing Su , Baoli Shi , Lili Wang , Qingwen Wang , Shujun Li
      Using PDMS (polydimethylsiloxane) as a basic polymeric matrix to the preparation of ethanol-permselective pervaporation membranes is a vibrant field of research. In this paper, a detailed study of the effects of the molecular weight of PDMS precursors and the content of the TEOS (tetraethyl orthosilicate) crosslinker on the degree of swelling in ethanol and ethanol contact angle is reported. Five PDMS precursors with molecular weights of 26.6 K, 35.5 K, 50.2 K, 71.7 K, and 110.4 K, and five crosslinking contents (1 wt%, 2 wt%, 5 wt%, 10 wt%, and 15 wt%) were chosen to prepare twenty five PDMS networks. Considering only the maximum tensile strength of the networks, the optimum molecular weight of the precursor was found to be 35.5 K and the optimum crosslinker content was 5 wt%. The average Young’s modulus of the PDMS network prepared under these conditions reached 0.63 MPa after using toluene to extract the network. Some uncrosslinked precursors always occur in the networks, and have some influence on the molecular weight of the precursors and the crosslinker content that is used. It was found that the content of the uncrosslinked precursors has direct effect on the contact angle of ethanol sessile drops at the surface of the extracted PDMS networks, and higher extraction corresponded to a smaller ethanol contact angle. A combined parameter (S), defined as the quotient of the extraction amount (AE ) and the tensile elastic modulus (EY ), gives a good linear relationship with the increase in weight of networks swelled in ethanol. This means that the degree of equilibrium swelling of the networks is simultaneously strongly influenced by the tensile modulus and the content of the uncrosslinked precursors.

      PubDate: 2014-09-03T00:59:50Z
  • Temperature- and pH-sensitive membrane formed from blends of
           poly(vinylidene fluoride)-graft-poly(N-isopropylacrylamide) and
           poly(acrylic acid) microgels
    • Abstract: Publication date: Available online 28 August 2014
      Source:Reactive and Functional Polymers
      Author(s): Xi Chen , Bowu Zhao , Peng Han , Weigui Fu , Li Chen
      Temperature- and pH-responsive membranes prepared from blends of poly(vinylidene fluoride)-graft-poly(N-isopropylacrylamide)(PVDF-g-PNIPAM) copolymer and poly(acrylic acid) (PAA) microgels in N, N-dimethylformamide (DMF) solution by phase inversion method. PAA microgels help PNIPAM chains largely enrich onto membrane surface. Furthermore, adding PAA microgels increases the porous size, porosity and hydrophilic property of the blend membrane. The membranes show temperature-sensitivity between 30 to 35°C, and pH- sensitivity between pH 3 and 5 on permeating aqueous solutions. Meanwhile, the blend membranes keep good antifouling property even if one of the hydrophilic components becoming hydrophobic in response to temperature or pH stimuli, which is superior to single-sensitive PVDF membrane.

      PubDate: 2014-09-03T00:59:50Z
  • Editors and Editorial Board
    • Abstract: Publication date: October 2014
      Source:Reactive and Functional Polymers, Volume 83

      PubDate: 2014-09-03T00:59:50Z
  • Water-soluble oxidized starch in complexation of Fe(III), Cu(II), Ni(II)
           and Zn(II) ions
    • Abstract: Publication date: October 2014
      Source:Reactive and Functional Polymers, Volume 83
      Author(s): Sanna Komulainen , Estibaliz Diaz , Johanna Kärkkäinen , Jouni Pursiainen , Paavo Perämäki , Marja Lajunen
      The structure of the bromate-oxidized wheat starch (OS) contains partly opened glucose units with carbonyl and carboxyl groups at C2-, C3- or C6-positions. OS with a variable degree of oxidation (DO) was studied in alkaline conditions as a water-soluble complexing agent for Fe(III), Cu(II), Ni(II) and Zn(II) ions, which are common in various wastewaters. Complexation was studied by inductively coupled plasma-optical emission spectrometry (ICP–OES) in a single metal ion or multi-metal ion solutions. The DO affected the efficiency of the complexation with metal ions. OS with the high DO (carboxyl and carbonyl DO of 0.72 and 0.23, respectively) complexed and held Fe(III) or Zn(II) ions in a soluble form effectively in 0.5mM single ion alkaline solution with the molar ratio of 0.65:1 of oxidized starch-to-metal ion (OS-to-M). The OS-to-M molar ratio of 1.3:1 was required to form a soluble complex with Cu(II) or Ni(II) ions. These complexes were thermally stable at the temperature range of 20–60°C. OS with the low DO (carboxyl and carbonyl DO 0.47 and 0.17, respectively) complexed Zn(II) ions highly, Cu(II) and Ni(II) ions poorly and Fe(III) ions only partly. In the multi-metal ion solution of OS the solubility of these metal ions improved with the increasing DO of starch, which followed the same tendency as was observed in the single metal ion systems. The increased molar ratio of OS-to-M improved the complexation and solubility of the metal ions in all multi-metal ion series. As the soluble multi-metal ion complexes were reanalyzed after 7days, all solutions had kept the high complexation and solubility of metal ions (ca. 90%). Complexation by OS did not show a selective binding of the ions in the multi-metal ion solution. It was concluded that the flexible, opened ring structure units of OS prevented the selective binding to metal ions but made the complexes highly stable. Titrimetric studies of OS–Fe(III) complexation showed that each anhydroglucose unit of OS had more than one coordination site and as the content of OS increased, the free sites coordinated to Fe(III) ions and formed cross-linked starch structures.

      PubDate: 2014-09-03T00:59:50Z
  • Donor–acceptor–donor polymers utilizing pyrimidine-based
    • Abstract: Publication date: October 2014
      Source:Reactive and Functional Polymers, Volume 83
      Author(s): Katie L. Winkel , Jamie R. Carberry , Leslie M. Wood , Makda Araya , Zachary W. Iszard , Travis Cantu , Benjamin Martin , Xiaopeng Li , Jennifer A. Irvin
      Pyrimidine acceptor groups were coupled with thienyl, 3,4-ethylenedioxythienyl (EDOT), and 3,4-(2,2-dibutylpropylenedioxy)thienyl (ProDOT-Bu2) donor groups in an attempt to synthesize stable n-doping polymers. Monomers were synthesized using a triorganoindium coupling reaction and characterized using nuclear magnetic resonance spectroscopy, X-ray crystallography, and electrochemical characterization techniques. The monomers undergo oxidative polymerization, with the alkylenedioxy-functionalized rings reducing oxidation and reduction potentials of monomer and polymer relative to the non-functionalized thiophene analogues, yielding electroactive polymers. The unsymmetrical nature of the monomers leads to unusual redox processes apparent during electrochemical polymerization. The polymer containing ProDOT-Bu2 groups was soluble in chloroform, while the other two polymers were insoluble. Band gaps were 1.6eV for the ProDOT-based polymer and 1.8eV for the EDOT-based polymer, which are comparable to other bisalkylenedioxyarylene-based polymers.

      PubDate: 2014-08-16T23:50:37Z
  • Poly(NIPAAm-co-β-cyclodextrin) microgels with drug hosting and
           temperature-dependent delivery properties
    • Abstract: Publication date: Available online 7 August 2014
      Source:Reactive and Functional Polymers
      Author(s): Marieta Constantin , Sanda Bucatariu , Paolo Ascenzi , Bogdan C. Simionescu , Gheorghe Fundueanu
      One of the most important drawbacks of the thermosensitive hydrogels based on N-isopropylacrylamide (NIPAAm) is the lack of functional groups able to specifically bind drugs; moreover, these hydrogels are not biodegradable. In order to overcome these inconveniences, poly(NIPAAm-co-β-cyclodextrin) (poly(NIPAAm-co-β-CD)) microgels were obtained by cross-linking polymerization of the corresponding monomers. β-CD was first functionalized with an appropriate amount of vinyl groups, thus acting both as a co-monomer with hosting properties and as a biodegradable cross-linker. The volume phase transition temperature (VPTT) of the microgels was determined under simulated physiological conditions by measuring the swelling degree and by microcalorimetry. The microgels, due to their small size and high porosity, possess a relative rapid swelling/deswelling rate around the human body temperature. The hydrogels were loaded with the model drug diclofenac by inclusion within cyclodextrin cavity and the release studies were performed under simulated physiological conditions, below and the above the VPTT. In the presence of α-amylase (from Aspergillus Oryzae), microgels have showed a low degradation rate (15% of initial weight after 7 days), the erosion occurring especially at the surface.

      PubDate: 2014-08-12T23:39:34Z
  • Synthesis and Optical, Electrical, and Thermoelectric Properties of Sodium
           Salts of Polyanilinesulfonic Acid
    • Abstract: Publication date: Available online 7 August 2014
      Source:Reactive and Functional Polymers
      Author(s): Isao Yamaguchi , Yusuke Sada
      Sodium salts of poly(aniline-5-sulfonic acid) (PAS), The PAS(Na)s, were obtained by the reaction of PAS with NaOH in water. The degree of sodium sulfonation of the PAS(Na)s depended on the feed amount of NaOH. The absorption peak of the PAS(Na)s, corresponding to an exciton transition generated by self-doping in the polymer backbone, decreased with the number of sodium sulfonated units. The PAS(Na)s were subjected to electrochemical oxidation, and the two oxidation peaks shifted to a lower potential as the degree of sodium sulfonation increased. The electrochemical reaction was accompanied by electrochromism. Thermoelectric measurements of the PAS(Na)s suggested that the majority of carriers were holes. The Seebeck coefficients (S’s) of the PAS(Na)s increased as the degree of sodium sulfonation of the polymers increased.

      PubDate: 2014-08-12T23:39:34Z
  • Synthesis and properties of polysiloxanes containing mixed functional
    • Abstract: Publication date: Available online 12 August 2014
      Source:Reactive and Functional Polymers
      Author(s): Hieronim Maciejewski , Joanna Karasiewicz , Agnieszka Dutkiewicz , Michał Dutkiewicz , Katarzyna Dopierała , Krystyna Prochaska
      An effective synthesis of polysiloxanes containing mixed functional groups was carried out using consecutive hydrosilylation of two different olefins. With the functionalization of polysiloxanes, we sought to obtain derivatives containing fluoroalkyl groups (with hydrophobic properties) and reactive groups capable of attaching a polysiloxane to the surface. Glycidyl and trimethoxysilyl groups were chosen for the study. All of the obtained derivatives were isolated and spectroscopically characterized. In the next stage of the study, glass plates were modified with functionalized polysiloxanes, both alone and with added silica sol, and their hydrophobic properties were determined by measuring contact angles. From the results, we determined the effect of functionalized polysiloxane structure on the hydrophobic properties of polysiloxane-modified surfaces.

      PubDate: 2014-08-12T23:39:34Z
  • New epoxy thermosets modified with amphiphilic multiarm star polymers as
           toughness enhancer
    • Abstract: Publication date: Available online 6 August 2014
      Source:Reactive and Functional Polymers
      Author(s): Carles Lagunas , Xavier Fernández-Francos , Francesc Ferrando , Marjorie Flores , Àngels Serra , Josep M. Morancho , Josep M. Salla , Xavier Ramis
      The synthesis and characterization of two novel amphiphilic multiarm star polymers with linear polyethylene glycol (PEG) and poly(ε-caprolactone) (PCL) arms and their use as toughening modifiers of epoxy anhydride thermosets are reported. The new star polymers were obtained by partial pegylation of a hyperbranched polyester and subsequent growth of PCL arms. The curing process was studied by calorimetry and thermomechanical analysis, demonstrating the accelerating effect and the influence on gelation of the hydroxyl terminal groups. The curing kinetics was analyzed by model-free and model-fitting methods. The final properties of the resulting materials were determined by thermal and mechanical tests. The addition of the star-like modifiers led only to notable improvement on impact strength in the material containing a 10% of the star with PCL and PEG arms, without compromising glass transition temperature and thermal stability. The morphology of the resulting materials depended on the structure of the toughness modifier used, as demonstrated by electron microscopy, but all modified thermosets obtained showed phase-separated morphologies with nanosized particles.

      PubDate: 2014-08-06T23:08:07Z
  • Editors and Editorial Board
    • Abstract: Publication date: September 2014
      Source:Reactive and Functional Polymers, Volume 82

      PubDate: 2014-08-02T22:23:04Z
  • UV-Light Assisted Single Step Route to Functional PEEK Surfaces
    • Abstract: Publication date: Available online 12 July 2014
      Source:Reactive and Functional Polymers
      Author(s): Ahmed Yousaf , Aleeza Farrukh , Zehra Oluz , Eylul Tuncel , Hatice Duran , Sema Yiyit Dogan , Turgay Tekinay , Habib ur Rehaman , Basit Yameen
      Polyether ether ketone (PEEK) is a thermoplastic polymer of high technological relevance and is composed of repeating phenyl ether and benzophenone units. In the present work we will demonstrate the potential of UV irradiation assisted generation of free radicals on the surface benzophenone units to graft a variety of polymer chains on the PEEK surface. Both “grafting-to” and “grafting-from” approaches were explored by using different monomers and polymers. Styrene, butyl acrylate (BA), vinyl phosphonic acid (VPA), acrylic acid (AA), polyacrylic acid (PAA) and monomethoxy terminated oligo(ethylene glycol)methacrylate (MeOEGMA) were successfully utilized for this purpose. The functionalized membranes were characterized by X-ray photoelectron spectroscopy (XPS), attenuated total reflectance Fourier-transformed Infrared (ATR-FTIR) spectroscopy, atomic force microscopy (AFM), and contact angle (CA) goniometry. PAA and PVPA functionalized PEEK surfaces exhibited pH responsive wettability behavior. PAA functionalized PEEK surfaces were further modified with lysine, which led to the controlled surface wettability over a broader pH range as compared to the simple PAA functionalized surface. The grafting with polyMeOEGMA rendered PEEK surface with nonfouling properties against bacterial growth. Employing this highly economical and simple method, the surface properties of PEEK can be modulated and tuned according to a specific application.

      PubDate: 2014-07-28T21:34:15Z
  • Preparation, characterisation and properties of sulphoxide modified
           polystyrene resins for solid-phase extraction of PtIV, RuIII and RuIV from
           hydrochloric acid
    • Abstract: Publication date: Available online 12 July 2014
      Source:Reactive and Functional Polymers
      Author(s): Michael Trautmann , Susanne Lubahn , Hans-Jürgen Holdt
      New sulphoxide modified resins were synthesized using poly(styrene-co-divinylbenzene) (PS-DVB) as matrix. Infrared spectroscopy and elemental analysis were used for characterisation. Solid-phase extraction of PtIV, RuIII and RuIV from acidic chloride solutions was performed via batch experiments. Influence of spacer length between sulphoxide and matrix (ethylene, hexamethylene), substitution of sulphoxide (R1: ethyl, hexyl, phenyl) and bead size of PS-DVB (spherical beads: d50<155 μm, d50<80 μm; powder: d50<30 μm) on adsorption was investigated subjected to acidity. Experimental results showed that ethyl substituted sulphoxide immobilised onto ground PS-DVB and hexamethylene spacer exhibited best adsorption properties. Different kinetic models and isotherms were fitted to the experimental data to identify extraction mechanism. PtIV was quantitative sorbed at [HCl]⩽0.1 mol/L whereas RuIII and RuIV sorption ranged between 90-95% at [HCl]⩾5 mol/L. Desorption was reached using a solution of 0.5M thiourea (Tu) in 0.1M HCl at 90°C. Separation of PtIV and RuIII occurred at [HCl]⩽0.1 mol/L whereas PtIV was extracted and RuIII remained in solution. A further separation was achieved by extracting PtIV and RuIV at 5M HCl followed by sequential elution of PtIV with concentrated HCl and RuIV with 0.5M Tu in 0.1M HCl at 90°C.

      PubDate: 2014-07-28T21:34:15Z
  • Synthesis and Characterization of Cross-Linked Molecularly Imprinted
           Polyacrylamide for the Extraction/Preconcentration of Glyphosate and
           Aminomethylphosphonic Acid from Water Samples
    • Abstract: Publication date: Available online 12 July 2014
      Source:Reactive and Functional Polymers
      Author(s): Kamilla da Mata , Marcela Zanetti Corazza , Fernanda Midori de Oliveira , Ana Lúcia de Toffoli , César Ricardo Teixeira Tarley , Altair Benedito Moreira
      The present study describes the synthesis of molecularly imprinted polyacrylamide and its applications for the selective adsorption of glyphosate (GP) and its degradation product, aminomethylphosphonic acid (AMPA). The molecularly imprinted polymers (MIPs) were prepared by polymerization in a homogeneous medium, which is known as the “in bulk” method. The reagents used for the synthesis were acrylamide (AAm) as the functional monomer, ethylene glycol dimethacrylate (EGDMA) as the cross-linking reagent, and azobisisobutyronitrile (AIBN) as the radical initiator. The selectivity of the MIPs was evaluated with non-imprinted polymers (NIPs) for each polymer synthesized without the template molecule. Polymer characterization was carried out by thermogravimetry (TG) analysis, Fourier-transform infrared spectroscopy (FT-IR), elemental analysis, and scanning electron microscopy (SEM). The experimental data on the adsorption kinetics were best explained by a pseudo-second-order kinetic model. The Langmuir-Freundlich nonlinear isotherm model for two adsorption sites had the best fit to the experimental data for glyphosate and AMPA. The maximum adsorption capacities were 3.37 and 4.74 mg g-1 for MIP-GP and MIP-AMPA, respectively. According to the relative selectivity (k’) values, higher selectivities for the analytes were observed in aqueous medium for the MIPs than for the NIPs.

      PubDate: 2014-07-28T21:34:15Z
  • Fabrication of composition-graded collagen/chitosan-polylactide scaffolds
           with gradient architecture and properties
    • Abstract: Publication date: Available online 21 July 2014
      Source:Reactive and Functional Polymers
      Author(s): Dengke Yin , Hua Wu , Chaoxu Liu , Jun Zhang , Ting Zhou , Jingjing Wu , Ying Wan
      Chitosan-polylactide (CH-PLA) copolymers with various polylactide percentages changing from around 14 to 40 wt% were synthesized. CH-PLAs were then blended with type-II collagen to fabricate layered collagen/CH-PLA scaffolds that are potentially suitable for the applications in articular cartilage repair. Based on combinatorial processing techniques involving layer-supraposition, thermal melting and freeze-drying, two types of stratified collagen/CH-PLA scaffolds were built. The content of collagen inside the scaffolds altered from the top layer to the bottom layer in a trend contrary to that of chitosan. One of them was fabricated using tripolyphosphate (TPP) as a single crosslinker and another type of scaffold was constructed via a dual-crosslinking pathway using TPP and genipin as two crosslinkers in a designated order. These collagen/CH-PLA scaffolds were found to have graded average pore-size and porosity, gradient swelling index and layer-dependent compressive modulus. The resulting scaffolds were thus partially similar to the articular cartilage extracellular matrix in composition, structure and property. In vitro cell culture on some optimized collagen/CH-PLA scaffolds for a period of time up to 3 weeks showed that the scaffolds were able to well support the growth of the seeded cells, suggesting that these collagen/CH-PLA scaffolds have promising potential for articular cartilage repair.

      PubDate: 2014-07-28T21:34:15Z
  • Electrochemical synthesis, characterization and capacitive properties of
           novel thiophene based conjugated polymer
    • Abstract: Publication date: Available online 21 July 2014
      Source:Reactive and Functional Polymers
      Author(s): Burcu Çelik , İlhami Çelik , Hacer Dolaş , Hakan Görçay , Yücel Şahin , A.Sezai Saraç , Kadir Pekmez
      In this paper, a novel thiophene based monomer, 1-(pyren-1-yl)-2,5-di(thiophen-2-yl)-1H-pyrrole, PThP, was synthesized and characterized by 1H NMR and 13C NMR spectroscopic methods. The electrochemical behavior and electropolymerization of this novel monomer were performed on pencil graphite electrode (PGE) by cyclic voltammetry. The effect of solvent, dopant, scan number and scan rate on the electropolymerization and properties of the conjugated polymer films were investigated. The capacitive properties of the poly(PThP) films were tested by electrochemical impedance spectroscopy (EIS). The highest specific capacitance value was calculaed for the conjugated polymer modified PGE that was obtained in 0.1 M tetrabutylammonium perchlorate/dichloromethane solution for 30 cycles at 25 mV/s scan rate as 25.45 mF cm-2. The surface morphologies of the conjugated polymer modified electrodes were determined by scanning electron microscopy (SEM).

      PubDate: 2014-07-28T21:34:15Z
  • Preparation, structural characterization, and flocculation ability of
           amphoteric cellulose
    • Abstract: Publication date: September 2014
      Source:Reactive and Functional Polymers, Volume 82
      Author(s): Hiroyuki Kono , Ryo Kusumoto
      A series of amphoteric celluloses (QACMCs) were prepared from sodium carboxymethyl cellulose (CMC) and 2,3-epoxypropyltrimethylammonium chloride (EPTMAC) with a cationic degree of substitution (DScat) of 0.24–1.06 and a carboxymethyl degree of substitution (DSani) of 0.60. The structures of the samples were characterized by FTIR and NMR spectroscopy, which revealed that DScat depended on the ratio of EPTMAC to CMC in the reaction mixture and that the substituent distribution of the cationic group at the C2, C3, and C6 positions of the QACMCs ranked as follows: C2>C6>C3. The QACMCs dissolved over a wide range of pH levels and exhibited flocculation ability against kaolin suspensions. In particular, the samples with high DScat exhibited excellent flocculation performance. In addition, the flocculation characteristics of the QACMCs depended on the pH of the kaolin suspension.

      PubDate: 2014-07-28T21:34:15Z
  • Encapsulation of Congo Red in carboxymethyl guar gum–alginate gel
    • Abstract: Publication date: September 2014
      Source:Reactive and Functional Polymers, Volume 82
      Author(s): Valeria E. Bosio , Sreyasree Basu , Fraqooue Abdullha , M. Elizabeth Chacon Villalba , Jorge A. Güida , Arup Mukherjee , Guillermo R. Castro
      Congo Red (CR) is a hydrophobic dye commonly used for diagnosis and potentially useful as therapeutic agent of beta amyloid plaques in neurodegenerative diseases. CR, as drug model, was encapsulated on Alginate–Carboxy Methyl Guar Gum (Alg–CMGG) blend microspheres. Guar gum 18% carboxymethylated (CMGG) derivative was synthesized in order to improve aqueous solubility, polymer blending and help reduce surface tension. The derivative was confirmed by FTIR spectroscopy, and elemental analysis. Surface tension of the new CMGG is reduced in about 50% compared with the native polymer. Lowering of Guar Gum (GG) aqueous solutions viscosity from 30,000cps to 350–400cps in case of CMGG is indicating pseudoplastic fluid behavior modifications. Vibrational spectroscopy analysis confirmed interactions among CR molecules in alginate–CMGG matrices ascribed largely to the aromatic motif of the dye and the biopolymer a polar regions. CR was encapsulated on 68/32% alginate/CMGG blend microspheres as the best formulation tested. The release of CR from the microspheres was not detected at pH=1.2 in 25min, but 62% of CR was found in the supernatant when the pH was raised to 7.4 at 37°C after 8h incubation.

      PubDate: 2014-07-28T21:34:15Z
  • Hydrophilic PVA-co-PE nanofiber membrane functionalized with iminodiacetic
           acid by solid-phase synthesis for heavy metal ions removal
    • Abstract: Publication date: September 2014
      Source:Reactive and Functional Polymers, Volume 82
      Author(s): Ying Lu , Zhihong Wu , Mufang Li , Qiongzhen Liu , Dong Wang
      A novel hydrophilic poly(vinyl alcohol-co-ethylene) (PVA-co-PE) nanofiber membrane for heavy metal ions removal was fabricated by the solid phase synthesis of iminodiacetic acid (IDA) on nanofiber membrane surfaces. The hydrophilic PVA-co-PE nanofiber membranes were activated with cyanuric chloride. The IDA was then covalently linked to the activated PVA-co-PE nanofiber membranes. The chemical structures of activated and functionalized PVA-co-PE nanofiber membranes were confirmed with FTIR–ATR. The morphology of PVA-co-PE nanofiber membranes were characterized with SEM. The increase in the amount of IDA on functionalized PVA-co-PE nanofiber membranes significantly improved the adsorption amount of Cu2+. The IDA functionalized PVA-co-PE nanofiber membranes demonstrated excellent adsorption capability of Cu2+, Co2+, Zn2+ and Ni2+. The adsorption of above heavy metal ions could be repeatedly regenerated by desorbing the ions adsorbed on nanofiber membranes. The novel IDA functionalized PVA-co-PE nanofiber membranes have great potential in the application of industry and drinking water treatment.

      PubDate: 2014-07-28T21:34:15Z
  • Biodegradable depsipeptide–PDO–PEG-based block copolymer
           micelles as nanocarriers for controlled release of doxorubicin
    • Abstract: Publication date: September 2014
      Source:Reactive and Functional Polymers, Volume 82
      Author(s): Juan Lv , Li Zhang , Musammir Khan , Xiangkui Ren , Jintang Guo , Yakai Feng
      Nowadays, biodegradable amphiphilic block copolymers with stable performance and adjustable structure have attracted the interests of researchers in the field of drug delivery. In this work, the triblock copolymer, P(SBMD-co-PDO)-b-PEG-b-P(SBMD-co-PDO), was successfully synthesized by ring-opening polymerization of 3(S)-sec-butyl-morpholine-2,5-dione (SBMD) and p-dioxanone (PDO) with poly(ethylene glycol) (PEG) as the initiator. In phosphate buffered solution (PBS), these copolymers could self-assemble into nano-sized micelles that have a hydrophobic P(SBMD-co-PDO) core surrounded by a hydrophilic PEG shell. Because of the strong hydrogen bonding and hydrophobic interactions, doxorubicin (DOX) was loaded into the micelles with high loading capacity (LC, up to 28.4%) and encapsulation efficiency (EE, up to 62.5%). The drug-loaded micelles showed sustained-release of DOX along with the hydrolytic degradation of the micelles in PBS. Therefore, these amphiphilic triblock copolymers have potential as drug matrix for controlled release.

      PubDate: 2014-07-28T21:34:15Z
  • Biodegradable macromolecular conjugates of citropin: Synthesis,
           characterization and in vitro efficiency study
    • Abstract: Publication date: October 2014
      Source:Reactive and Functional Polymers, Volume 83
      Author(s): Marcin Sobczak , Wojciech Kamysz , Wiktor Tyszkiewicz , Cezary Dębek , Ryszard Kozłowski , Ewa Olędzka , Urszula Piotrowska , Grzegorz Nałęcz-Jawecki , Andrzej Plichta , Daria Grzywacz , Elwira Furtak
      The effective synthesis of citropin–polymer conjugates was described in this paper. The obtained biodegradable polymeric matrices and polymeric conjugates were characterized using 1H or 13C NMR and Fourier transform infrared spectroscopies, gel permeation chromatography and scanning electron microscopy. Toxicity of polymers was evaluated with bacterial luminescence test and two protozoan assays. The in vitro release study of citropin from the obtained conjugates was investigated. The preliminary results of antimicrobial activity of the obtained macromolecular conjugates against Bacillus anthracis, Enterococcus hirae and Staphylococcus aureus were also discussed. The peptide had a high level of antimicrobial activity during 3–5weeks of the degradation process. The development of biodegradable citropin systems should be of a great interest in the delivery systems of antimicrobial agents.

      PubDate: 2014-07-28T21:34:15Z
  • Synthesis of poly(2,6-dimethyl-1,4-phenylene oxide) derivatives containing
           hydroxyl and amino groups by oxidative coupling copolymerization
    • Abstract: Publication date: October 2014
      Source:Reactive and Functional Polymers, Volume 83
      Author(s): Shigeki Habaue , Shigeyuki Iwai , Hidekazu Kubo , Koya Nagura , Tomohiro Watanabe , Yasuhiro Muraki , Yasuhiro Tsutsui
      Oxidative coupling copolymerization between 2,6-dimethylphenol (DMP) and functional monomers containing hydroxyl and amino groups, 2-hydroxymethyl-6-methylphenol and 2-(4-methylphenylamino)methyl-6-methylphenol, was carried out with a Cu catalyst under an O2 atmosphere. The polymerization was significantly affected by the polymerization solvent used, and the copolymers were effectively obtained by polymerization in polar solvents, such as a mixed solvent system containing methanol. The obtained copolymer containing hydroxyl groups was further transformed into polymers containing ester and urethane groups, which were used as additives for the fabrication of polyurethane films. The tensile properties of the films containing the obtained copolymers were significantly improved compared to those of films prepared without an additive, as well as films containing the homo-polymer of DMP.

      PubDate: 2014-07-28T21:34:15Z
  • Synthesis and characterization of a main-chain donor–acceptor type
           low-bandgap polymer by post-functionalization of a poly(arylene
    • Abstract: Publication date: October 2014
      Source:Reactive and Functional Polymers, Volume 83
      Author(s): Wenyi Huang
      I report a facile synthetic route for synthesizing a main-chain donor–acceptor type polymer containing strong electron donating dialkylamino groups and strong electron accepting 1,1,4,4-tetracyanobuta-1,3-diene (TCBD) units. To accomplish this, an electron donating monomer 4,6-diethynyl-N,N,N,N-tetrahexylbenzene-1,3-diamine was successfully synthesized by converting two carbaldehyde groups in the corresponding monomer into acetylene groups using lithium trimethylsilyldiazomethane via Colvin rearrangement. This electron donating monomer was then polymerized with a carbonyl-activated diiodide monomer to afford an electron-donating π-conjugated precursor polymer with a reasonably high molecular weight, which was further reacted with TCNE via cycloaddition/retroelectrocyclization reaction under mild conditions to afford the target polymer with a low bandgap energy ( E g opt = 1.40 eV and E g CV = 1.10 eV ) arising from strong intramolecular charge-transfer interactions between electron donors and acceptors in the polymer.

      PubDate: 2014-07-28T21:34:15Z
  • Use of poly(3-methylthio)thiophene blends for direct laser tracing and
           bulk heterojunction solar cells
    • Abstract: Publication date: October 2014
      Source:Reactive and Functional Polymers, Volume 83
      Author(s): Massimiliano Lanzi , Luisa Paganin , Filippo Pierini , Francesco Errani , Francesco Paolo Di-Nicola
      In this article we demonstrate the use of a blend made of two regioregular polythiophenic derivatives, namely poly(3-methylthio)thiophene and poly(3-hexyl)thiophene, to obtain conductive traces by the simple laser exposure of their thin films to a suitable laser source. The polymeric blend was also tested as a photoactive layer for BHJ solar cells, showing an improved surface morphology and a wider absorption spectrum, thus resulting in an enhanced photovoltaic performance. In the standard condition normally used for the cell preparation, we obtained a 3.16% power conversion efficiency. The device showed good reproducibility and stability over time.

      PubDate: 2014-07-28T21:34:15Z
  • Evaluation of hybrid polymer containing iron oxides as As(III) and As(V)
           sorbent for drinking water purification
    • Abstract: Publication date: October 2014
      Source:Reactive and Functional Polymers, Volume 83
      Author(s): Daniel Ociński , Irena Jacukowicz-Sobala , Jerzy Raczyk , Elżbieta Kociołek-Balawejder
      The objective of this paper was to evaluate the possibility of utilization of a novel hybrid polymer containing iron oxides as an arsenate and arsenite sorbent in water treatment. This material was primarily obtained as a by-product in the water de-ironing process by means of N-chlorosulfonamide polymers. The sorption properties of the hybrid polymer, including pH and coexisting ions’ influence on arsenic removal efficiency, were examined using kinetic and equilibrium experiments in a batch regime. In the column process, conducted with As-spiked natural water containing both As(III) and As(V), the breakthrough of the sorbent bed occurred after the solution amounting to about 4800 bed volumes passed through the column. The regeneration and re-use of the sorbent with NaOH and NaCl solution was also studied, indicating the possibility of repeated use of the sorbent with only a slight decrease in its sorptive properties for four cycles.

      PubDate: 2014-07-28T21:34:15Z
  • Non-cytotoxic conductive carboxymethyl-chitosan/aniline pentamer hydrogels
    • Abstract: Publication date: September 2014
      Source:Reactive and Functional Polymers, Volume 82
      Author(s): Lin Zhang , Yan Li , Longchao Li , Baolin Guo , Peter X. Ma
      Cytocompatible electrically conducting hydrogels based on amphoteric carboxymethyl chitosan (CMCS) and aniline oligomers with bioactive molecule delivery properties were presented. A series of conductive CMCS hydrogels with different aniline pentamer (AP) content were synthesized by a one-pot reaction with the combination of grafting and crosslinking reaction via glutaraldehyde. The conductivities of the swollen hydrogels are between 1.14×10−4 and 4.23×10−4 S/cm by tuning the AP content. Swelling ratio was controlled by the AP content and crosslinking degree of the hydrogels. The hydrogels showed absorption capacity of diclofenac sodium (DCS) as a model molecule and released DCS in a controlled manner. Morphologies and mechanical properties of the hydrogels were characterized by SEM and rheometer, respectively. The biocompatibility of the hydrogels was confirmed by C2C12 myoblast cells using Live/Dead assay and Alamar blue assay. These conducting hydrogels with controlled release capacity as bioactive scaffolds have potential application for tissue regeneration.

      PubDate: 2014-07-28T21:34:15Z
  • Enzyme immobilization on smart polymers: Catalysis on demand
    • Abstract: Publication date: October 2014
      Source:Reactive and Functional Polymers, Volume 83
      Author(s): Giuseppe Cirillo , Fiore Pasquale Nicoletta , Manuela Curcio , Umile Gianfranco Spizzirri , Nevio Picci , Francesca Iemma
      A new approach for the synthesis of hydrogel films with thermo-sensitive enzymatic activity is reported. Pepsin (PEP) was covalently immobilized on thermo-responsive hydrogels by radical polymerization in the presence of N-isopropylacrylamide and poly-(ethylene glycol) dimethacrylate 750, acting as functional monomer and crosslinking agent, respectively. Hydrogels showing lower critical solution temperatures between 32.9 and 36.1°C were synthesized by UV-irradiation of reaction batches differing in the PEP/monomers ratio. The derivatization degree of the hydrogels was expressed as mg of PEP per gram of matrix and found to be in the range of 6 to 11% as assessed by Lowry method. Scanning electron microscopy analysis and water affinity evaluation allowed to highlight the porous morphology and thermo-responsivity of hydrogels as a function of temperature. Using bovine serum albumin as a substrate, kinetics parameters were determined by Lineweaver–Burk plots and the catalyst efficiency evaluated. The influence of temperature on enzyme activity, as well as the thermal stability and reusability of devices, were also investigated.

      PubDate: 2014-07-28T21:34:15Z
  • Preparation and characterization of p-tert-butyl thiacalix[4]arene
           imbedded flexible polyurethane foam: An efficient novel cationic dye
    • Abstract: Publication date: October 2014
      Source:Reactive and Functional Polymers, Volume 83
      Author(s): Abbas Mohammadi , Moslem Mansour Lakouraj , Mehdi Barikani
      In this study, a new type of flexible polyurethane foam containing p-tert-butyl thiacalix[4]arene (TC4A) macrocycle was synthesized. TC4A macrocycle was incorporated into polyurethane foam as a part of crosslinking agent as well as glycerol. Structural, morphological, thermal and mechanical properties of this prepared foam were studied and compared with a polyurethane foam based on only glycerol as crosslinking agent, by Fourier transform infrared (FTIR), Scanning electron microscopy (SEM), Thermal gravimetric analysis (TGA), and dynamic mechanical thermal analysis (DMTA). The effect of introduction of TC4A crosslinker on cream time, rise time, apparent density, and water absorbency of the PU foams was evaluated. Moreover, it was shown that new TC4A-based polyurethane foam (TC-PUF) can be a high performance adsorbent for removal of malachite green from aqueous media using batch adsorption technique. The adsorption results indicated that TC-PUF has a high adsorption capacity of 58.82mg/g for malachite green due to the presence of TC4A macrocycles in the structure of polyurethane foam. The kinetics of adsorption of malachite green was also investigated using the pseudo-first-order and pseudo-second-order kinetic models. The results of kinetic studies showed that the adsorption of malachite green onto TC-PUF followed pseudo-second-order kinetic model.

      PubDate: 2014-07-28T21:34:15Z
  • Preparation of novel antimicrobial polymer colloids based on (+)-usnic
           acid and poly(vinylbenzyl chloride)
    • Abstract: Publication date: October 2014
      Source:Reactive and Functional Polymers, Volume 83
      Author(s): R. Bengü Karabacak , Turgay Tay , Merih Kıvanç
      A novel antimicrobial colloidal system based on (+)-usnic acid, an important natural antimicrobial molecule, and poly(vinylbenzyl chloride) (PVBC) colloids was synthesized. The chloromethyl functionality on poly(vinylbenzyl chloride) was utilized to bind (+)-usnic acid. To achieve this, the resultant polymer colloids were treated with (+)-usnic acid in triethylamine. The (+)-usnic acid bound particles (PVBC/Us and PVBC/Us/Us) had positive zeta potential values in the range of pH 3–12. The antimicrobial activity of the (+)-usnic acid loaded colloidal particles (PVBC/Us and PVBC/Us/Us) was tested against various microorganisms such as Listeria monocytogenes, Staphylococcus aureus, Enterococcus faecalis, Escherichia coli, Pseudomonas aeruginosa, Salmonella typhimurium, and Klebsiella pneumonia, Candida albicans and Candida glabrata. P. aeruginosa and E. coli appeared to be the most sensitive microorganism compared to the others. The minimum inhibitory concentration (MIC) was determined using different colloid concentrations. The resultant (+)-usnic acid loaded colloids showed high antimicrobial activity against many microorganisms with MIC values down to 0.12mgcolloid/mL. While PVBC/Us/Us colloids had bacteriostatic effect against all the tested microorganisms, PVBC/Us colloids had against only four of them. Furthermore, PVBC/Us/Us colloids showed bactericidal effect against P. aeruginosa and E. coli with minimum bactericidal concentration (MBC) values of 0.94 and 3.75mg colloid/mL, respectively. In contrast, (+)-usnic acid had no activity on its own. Owing to the small and uniform sizes and high surface areas, (+)-usnic acid loaded colloids afforded greater contact area with the bacterial cell.

      PubDate: 2014-07-28T21:34:15Z
  • Effect of photofunctional organo anion-intercalated layered double
           hydroxide nanoparticles on poly(ethylene terephthalate) nonisothermal
           crystallization kinetics
    • Abstract: Publication date: October 2014
      Source:Reactive and Functional Polymers, Volume 83
      Author(s): Tianchi Cao , Yang Feng , Guangming Chen , Cun-Yue Guo
      Very recently, we report a facile preparation and strong UV-shielding function of poly(ethylene terephthalate) (PET) nanocomposites using 4,4′-diaminostilbene-2,2′-disulfonic acid anion-intercalated layered double hydroxide (LDH_DDA). Herein, the effect of the photofunctional organo anion-intercalated LDH nanoparticles on nonisothermal crystallization kinetics of PET is reported by differential scanning calorimetry technique. First, the nonisothermal crystallization behaviour is discussed by several basic parameters including crystallization peak temperature, relative degree of crystallinity with temperature or time, and half-time of crystallization. Then, Avrami and Jeziorny method, as well as Mo model were applied for the PET/LDH_DDA nanocomposites. Finally, the crystallization activation energy was investigated by Kissinger method and Flynn conversion. The results reveal that the incorporation of LDH_DDA nanoparticles acted as nucleating agent and significantly accelerated the PET nonisothermal crystallization process, whereas had little effect on the three-dimensional growth pattern of spherulites.

      PubDate: 2014-07-28T21:34:15Z
  • Immobilization of 3-hydroxybenzoate 6-hydroxylase onto functionalized
           electrospun polycaprolactone ultrafine fibers: A novel heterogeneous
    • Abstract: Publication date: September 2014
      Source:Reactive and Functional Polymers, Volume 82
      Author(s): Tiyaporn Srisook , Thammasit Vongsetskul , Jeerus Sucharitakul , Pimchai Chaiyen , Pramuan Tangboriboonrat
      3-Hydroxybenzoate 6-hydroxylase (3HB6H), an enzyme that catalyzes regiospecific para-hydroxylation of aromatic compounds, was successfully immobilized onto electrospun polycaprolactone (PCL) ultrafine fibers (424±99nm in diameter). The fibers were fabricated from 13% w/w PCL (MW ∼8×104 g/mol) dissolved in a mixed solvent of formic acid (25% v/v) and acetic acid (75% v/v) at an applied voltage of 16kV and a fiber collection distance of 12.5cm. Before being immobilized with 3HB6H, the surface of electrospun PCL fibers was functionalized by reacting with ethylenediamine activated with 5% v/v glutaraldehyde using aluminum sulfate as a catalyst. Effects of the immobilization process on pH tolerance and thermal stability of 3HB6H were investigated. Results indicated that 3HB6H immobilized onto PCL fibers could tolerate the changes in temperature and pH better than the free enzyme could. Therefore, the 3HB6H-immobilized PCL fibers are potentially useful as a heterogeneous catalyst under the conditions in which free 3HB6H could not endure.

      PubDate: 2014-06-18T16:38:55Z
  • Synthesis and investigation of monomodal hydroxy-functionalized PEG
           methacrylate based copolymers with high polymerization degrees.
           Modification by “grafting from”
    • Abstract: Publication date: September 2014
      Source:Reactive and Functional Polymers, Volume 82
      Author(s): Paulina Maksym-Bębenek , Tadeusz Biela , Dorota Neugebauer
      The synthesis of monomodal copolymers with poly(ethylene glycol) (PEG) side chains from commercial poly(ethylene glycol) methacrylates (PEGMA) by atom transfer radical polymerization (ATRP) is verified. Two hydroxy-functionalized PEGMA macromonomers (520g/mol and 360g/mol) were copolymerized with methyl methacrylate (MMA) using various initial feed (1.5/98.5–50/50mol.%). The copolymers P(MMA-co-PEGMA) with high degree of polymerization, e.g. 100–275 of repeating units in the backbone including 7–56 PEG side chains, were obtained. The relative reactivity ratios of PEGMA and MMA determined by the Jaacks method indicated slightly faster incorporation of macromonomer into polymeric chain than MMA (r MMA =0.79; r PEGMA =1.27). The polymers containing at least 17mol.% of PEGMA units were water-soluble and exhibited clouding point at temperature in a broad range of 39–70°C. The temperature-sensitive effect makes these polymers as a potential carriers in drug delivery systems. In the case of copolymers insoluble in water, a three-step procedure, including esterification to ATRP multifunctional macroinitiators, ATRP of tert-butyl methacrylate (tBMA) by grafting from, deprotection of carboxylic groups by removing tert-butyl groups, was applied to extend PEG grafts and expand the content of hydrophilic fraction (32–94mol.%), what efficiently developed polymer solubility in polar solvents giving possibility for the future biomedical applications.
      Graphical abstract image Highlights

      PubDate: 2014-06-18T16:38:55Z
  • Synthesis and characterization of PS-b-PGMA diblock copolymer and its
           interaction with blood proteins and donepezil
    • Abstract: Publication date: September 2014
      Source:Reactive and Functional Polymers, Volume 82
      Author(s): Leman Buzoglu , Esra Maltas , Mustafa Ersoz , Salih Yildiz
      Biocompatible polystyrene-block-poly(glycidyl methacrylate) (PS-b-PGMA) diblock copolymers with different molecular weights were synthesized via atom transfer radical polymerization (ATRP), homopolymers of styrene with narrow molecular weight distribution were prepared and used macroinitiators for block copolymerization. The effect of time, temperature, solvent, and in-feed ratio on the synthesis of the polymer was examined. Human serum albumin (HSA), bovine serum albumin (BSA), globulin (Glb) and hemoglobin (Hb) which are intrinsically fluorescent blood proteins were interacted with the synthesized PS-b-PGMA diblock copolymers. A calibration curve equation was used to calculate the amount of immobilized proteins on the diblock copolymers through fluorescence spectroscopy. These occurred at wavelengths of 280nm and 324nm, which correspond to the excitation and emission wavelengths of tyrosine and tryptophan residues. Following the interaction of PS-b-PGMA diblock copolymer with the blood proteins, the protein was subjected to a pharmaceutical active substance, donepezil. The copolymers, homo polymers and protein-polymers along with the drug interactions were characterized using 1H NMR, FT-IR and gel permeation chromatography (GPC), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDX).
      Graphical abstract image Highlights

      PubDate: 2014-06-18T16:38:55Z
  • Synthesis of Poly(N-isopropylacrylamide)-b-Poly(ε-caprolactone) and
           Its Inclusion Compound of β -Cyclodextrin
    • Abstract: Publication date: Available online 23 May 2014
      Source:Reactive and Functional Polymers
      Author(s): Zhongyu Duan , Li Zhang , Huili Wang , Bing Han , Binyuan Liu , Il Kim
      Well-defined amphiphilic poly(N-isopropylacrylamide)-b-Poly(ε-caprolactone) (PNIPAM-b-PCL) block copolymers have been successfully prepared in two steps. PNIPAM−OH is firstly prepared by using 4,4’-azobis(4-cyano-1-pentanol) as bifunctional initiator, and then PNIPAM-b-PCL copolymer is synthesized via a ring-opening polymerization of CL using PNIPAM−OH as a macro-initiator in the presence of stannous octoate as a catalyst. The PNIPAM-b-PCL copolymers self-assemble to form spherical micelles of 50-130 nm in diameter, which can be modulated by the chain length of PCL block. The inclusion complexes are fabricated by treating PNIPAM-b-PCL with β-cyclodextrin and they are characterized by infrared and 1H NMR spectroscopies, x-ray powder diffraction, thermogravimetric analysis, and differential scanning calorimetry.
      Graphical abstract image Highlights

      PubDate: 2014-06-18T16:38:55Z
  • Synthesis and Properties of Soluble Cross-linkable Fluorinated
    • Abstract: Publication date: Available online 12 June 2014
      Source:Reactive and Functional Polymers
      Author(s): Hongyan Yao , Yunhe Zhang , Kaiyuan You , Yu Liu , Ying Song , Shanyou Liu , Shaowei Guan
      A series of high molecular weight soluble fluorinated cross-linkable co-polyimides (Co-PIs) were synthesized from 1,3-bis(2-trifluoromethyl-4-aminophenoxy)-5-(2,3,4,5-tetrafluorophenoxy) benzene (6FTFPB), 1,4-bis(4-amino-2-trifluoromethylphenoxy)benzene (6FAPB), 1,4-bis(4-amino-2-trifluoromethyl-phenoxy)-2-(3’-trifluoro-methylphenyl)benzene (m-3F-6FAPB) and 4,4’-(hexafluoroisopropylidene)diphthalic anhydride (6FDA). The weight-average molecular weights (Mws) and polydispersities of the co-polyimides were in the range 5.53-7.24 and 1.71-2.04, respectively. By adjusting the feed ratio of diamines, the refractive indices of Co-PIs films were exactly tuned in the range of 1.5203-1.5574 at 633 nm. The co-polyimides showed outstanding solubility in organic solvents and high thermal stability (5% thermal weight-loss temperature beyond 525 °C). Meanwhile, the films had excellent mechanical properties with high tensile strength of 100-108 MPa, Young’s modulus of 3.3-4.2 GPa and elongations at break of 8-15%. Polymers in the form of cast and spun films could be cross-linked by thermal curing at 260 °C. After curing, the Co-PIs films showed excellent chemical resistance, high glass transition temperatures above 270 °C, higher mechanical properties and thermal stability (5% thermal weight-loss temperature beyond 540 °C) and low dielectric constant in the range of 2.37-2.70.

      PubDate: 2014-06-18T16:38:55Z
  • Synthesis of polysaccharide derivatives bearing bromobenzoate pendants for
           use as chiral auxiliaries
    • Abstract: Publication date: Available online 13 June 2014
      Source:Reactive and Functional Polymers
      Author(s): Tomoyuki Ikai , Kazuma Kimura , Katsuhiro Maeda , Shigeyoshi Kanoh
      Cellulose and amylose derivatives bearing bromobenzoate pendants were synthesized as chiral auxiliaries to create optically active biaryl compounds through Suzuki–Miyaura cross-coupling with naphthalen-1-ylboronic acids. The regioselectively substituted polysaccharide derivatives bearing 2-bromobenzoate pendants at the 6-position of the glucose unit exhibited higher diastereoselectivity than did the corresponding monosaccharide-based chiral auxiliary and the non-regioselectively substituted polysaccharide derivative bearing 2-bromobenzoates at the 2,3,6-positions. These results suggest that the chiral induction by the regioselectively substituted polysaccharide-based auxiliaries is mainly based on regular higher-order structures, such as one-handed helical structures.

      PubDate: 2014-06-18T16:38:55Z
  • Synthesis of Novel Copper Ion-Selective Material Based on Hierarchically
    • Abstract: Publication date: Available online 14 June 2014
      Source:Reactive and Functional Polymers
      Author(s): Talitha Oliveira Germiniano , Marcela Zanetti Corazza , Mariana Gava Segatelli , Emerson Schwingel Ribeiro , Maria Josefa Santos Yabe , Evgeny Galunin , César Ricardo Teixeira Tarley
      A novel hierarchically imprinted cross-linked poly(acrylamide-co-ethylene glycol dimethacrylate) using a double-imprinting approach for the Cu2+ selective separation from aqueous medium was prepared. In the imprinting process, both Cu2+ ions and surfactant micelles (cetyltrimethylammonium bromide - CTAB) were employed as templates. The hierarchically imprinted organic polymer named (IIP-CTAB), single-imprinted (IIP-no CTAB) and non-imprinted (NIP-CTAB and NIP-no CTAB) polymers were characterized by SEM, FTIR, TG, elemental analysis and textural data from BET (Brunauer–Emmett–Teller) and BJH (Barrett-Joyner-Halenda). Compared to these materials, IIP-CTAB showed higher selectivity, specific surface area and adsorption capacity towards Cu2+ ions. Good selectivity for Cu2+ was obtained for the Cu2+/Cd2+, Cu2+/Zn2+ Cu2+/Co2+ systems when IIP-CTAB was compared to the single-imprinted (IIP-no CTAB) and non double-imprinted polymer (NIP-CTAB), thereby confirming the improvement in the polymer selectivity due to double-imprinting effect. For adsorption kinetic data, the best fit was provided with the pseudo-second-order model for the four materials, thereby indicating the chemical nature of the Cu2+ adsorption process. Cu2+ adsorption under equilibrium was found to follow dual-site Langmuir-Freundlich model isotherm, thus suggesting the existence of adsorption sites with low and high binding energy on the adsorbent surface. From column experiments 600 adsorption-desorption cycles using 1.8 mol L-1 HNO3 as eluent confirmed the great recoverability of adsorbent. The synthesis approach here investigated has been found to be very attractive for the designing of organic ion imprinted polymer and can be expanded to the other polymers to improve performance of ion imprinted polymers in the field of solid phase extraction.

      PubDate: 2014-06-18T16:38:55Z
  • Atom Transfer Radical Polymerization of Glycidyl Methacrylate Followed by
           Amination on the Surface of Monodispersed Highly Crosslinked Polymer
           Microspheres and the Study of Cation Adsorption
    • Abstract: Publication date: Available online 18 June 2014
      Source:Reactive and Functional Polymers
      Author(s): Lisha Wang , Fengcai Li , Minde Yao , Tian Qiu , Weihua Jiang , Li-Juan Fan
      The introduction of reactive groups on the surface of monodispersed highly crosslinked poly(styrene-divinylbenzene) (PSDVB) microspheres was accomplished in two steps. The first step requires immobilizing the initiating groups by a Friedel-Craft acylation between 2-chloropropionyl chlorides and the phenyl groups on the spheres. The second step requires the atom transfer radical polymerization (ATRP) of glycidyl methacrylate (GMA) to obtain spheres (PSDVB-g-PGMA) with epoxy groups on the surface. To demonstrate the feasibility of introducing functionality, the epoxy groups were ring-opened by ethylenediamines, resulting in spheres with amino functionality (PSDVB-g-PGMAEDA). The final spheres were found to have an adsorption capacity of 0.66 mmol/g in the Cu2+ adsorption experiments, as a preliminary application study.
      Graphical abstract image Highlights

      PubDate: 2014-06-18T16:38:55Z
  • Optically active amino acid-based polyacetylenes: Effect of tunable
           helical conformation on infrared emissivity property
    • Abstract: Publication date: September 2014
      Source:Reactive and Functional Polymers, Volume 82
      Author(s): Xiaohai Bu , Yuming Zhou , Zhenjie Chen , Man He , Tao Zhang
      Chiral amino acid-based monosubstituted acetylene monomers [N-tert-butoxy-carbonyl-l-phenylalanine-N′-propargylamide (LP), and N-tert-butoxycarbonyl-l-serine-N′-propargylamide (LS)] were (co)polymerized with rhodium zwitterion catalyst in THF to afford helical polyacetylenes (PAs) with moderate molecular weights (4400–14,800) in good yields. The optically active PA copolymers were soluble in common organic solvents and proven to adopt predominately single-handed helical conformations according to their intense Cotton effect and large specific rotations. Various contents of amino acid units in side chains facilitated controllable helical secondary structure while the helix was primarily stabilized by hydrogen bonding and steric repulsion between the substituents. Intramolecular hydrogen bonds constructed between hydroxyl and amide groups, in particular, played a significant role in adjusting the helicity and orderliness of the helix. The infrared emissivity values of the PAs at wavelength of 8–14μm were measured and the correlation between helical conformations and their effect on infrared emission were systematically investigated. The results showed that more well-ordered and compact screw-sense could enhance the performance of organic polymers in lowering their infrared emissivity. Among all the as-prepared PAs, poly(LP50-co-LS50) exhibited the lowest infrared emissivity value (ε 25 =0.632) and possessed excellent resistance against heat.
      Graphical abstract image Highlights

      PubDate: 2014-06-18T16:38:55Z
  • One-pot synthesis of TBTA-functionalized coordinating polymers
    • Abstract: Publication date: September 2014
      Source:Reactive and Functional Polymers, Volume 82
      Author(s): Alireza Movahedi , Kasper Moth-Poulsen , Johnas Eklöf , Magnus Nydén , Nina Kann
      A one-pot method for the functionalization of polyvinylbenzyl chloride with a tris-(benzyltriazolylmethyl)amine (TBTA) ligand via the copper-catalyzed azide–alkyne cycloaddition reaction (CuAAC) is reported, where the ligand is constructed simultaneously with its attachment to the polymer backbone. A hydrophobic TBTA polymer as well as co-polymers containing TBTA ligands were also prepared to demonstrate the possibility of tailoring the properties of the polymers. The polymers were characterized with FT-IR and NMR spectroscopy, elemental analysis, contact angle measurement, differential scanning calorimetry and thermal gravimetric analysis. The metal coordinating properties of films prepared from the polymers was also demonstrated using X-ray photoelectron spectroscopy and their structures inspected by scanning electron microscopy.

      PubDate: 2014-06-18T16:38:55Z
  • Preparation and chemical properties of π-conjugated
           poly(1,10-phenanthroline-3,8-diyl)s with crown ether subunits
    • Abstract: Publication date: September 2014
      Source:Reactive and Functional Polymers, Volume 82
      Author(s): Hiroki Fukumoto , Yumiko Kase , Take-aki Koizumi , Takakazu Yamamoto
      π-Conjugated polymers consisting of 1,10-phenanthroline units and crown ether subunits (Poly-1, Poly-2, and Poly-3) were prepared by dehalogenation polycondensation of the corresponding dibromo monomers using a zero-valent nickel complex as a condensing agent. They were characterized by elemental analysis, 1H NMR and UV–Vis spectroscopies, and cyclic voltammetry (CV). They were partly soluble in CHCl3, and the number average molecular weight of the soluble part of Poly-2, which had 15-crown-5 subunits, was estimated to be 5300. The polymers exhibited UV–Vis peaks at approximately λ max =360nm, which was reasonable. Complexation with [Ru(bpy)2]2+ and alkaline metal ions made the polymer soluble in organic solvents. The complexation of [Ru(bpy)2]2+ to the 1,10-phenanthroline unit proceeded quantitatively, and the [Ru(bpy)2]2+ complexes exhibited CV curves characteristic of [Ru(N-N)3]2+ complexes.

      PubDate: 2014-06-18T16:38:55Z
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